Beruflich Dokumente
Kultur Dokumente
ISSN: 2278-0181
Vol. 3 Issue 1, January - 2014
IJE
RT
Keywords: Heavy metals, cassava peel activated carbon, adsorption isotherm, kinetic studies, isotherm studies.
1.0 INTRODUCTION
Industrialization is the back bone of every nations economy and the enhancement of citizenry well-being.
However the negative impacts of industrial developments especially in the developing countrieshave become sources of
concerns. These industrial developments comes along with the generation of unwanted by-products, which in most
cases are discharged into the ecological systems leading to different types of pollutions. Subsequent negative impact of
such pollution is felt not only by human beings but also by living organisms including plants. For instance, the
introduction of untreated effluents into rivers and water bodies leads to build-up of poisonous contaminants (water
pollution) like heavy metals (Hg, Pb, Cu, Zn, etc.) among others. Unlike organic pollutants, the majority of which are
susceptible to biological degradation, heavy metal ions do not degrade into harmless end products (Gupta and Sharma,
2001).
When heavy metals enter the food chain, they builds up and cause mental retardation, reduction in
haemoglobin, production and interference with normal cellular metabolism and consequently may damage the nervous
system. Furthermore, strong exposure to heavy metals may cause gastric pain, nausea, vomiting, severe diarrhea,
hemorrhage and affect the digestive tract and lungs (Klaassenet al., 2001; Mohanty et al., 2005). Thus, it is desirable to
remove toxic heavy metals from wastewater, probably via adsorption process, before it is discharged into the
environment.
One of the difficulties in describing the adsorption of heavy metals from waste streams is that wastewater
contains more than one types of heavy metals. When several components are present, interference and competition
phenomena for adsorption sites occur (Janget al., 2001; Abdullah, et al., 2010). Study on palm kernel shell activated
carbon has shown that competitive adsorption for active sites on the carbon surface resulted in a reduction of the
overall uptake capacity of reactive dyes (Nourouziet al., 2009).
In this study,the adsorption process of a cassava peel activated carbondeveloped and used as low-cost
adsorbent to remove zinc, copper, iron and lead from electroplating wastewater has been investigated by evaluating the
environmentalparameters affecting the adsorption process such as pH, agitation time, metal, adsorbent dosage and
agitation speed and fitting theequilibrium adsorption data usingLangmuir, Freundlich, Dubinin-Radushkevich and
Temkin models
2.0 MATERIALS AND METHODS
2.1 Carbonization of Cassava Peel
The dried peels were crushed into powder form and 15 g of the samples were weighed into six different clean
and pre-weighed crucibles, which were then introduced into the hot zone of amuffle furnace. The furnace temperature
was increased at a rate of 10 oC/min from the room temperature. The peels were carbonized at different temperatures
(250, 300, 350, and 400 oC). The samples were held at this temperature for various times (15, 30, 45, and 60 min) in
order to establish optimum conditions. The content was then removed from the muffle furnace after the set period and
IJERTV3IS10190
www.ijert.org
25
cooled in an open air for one hour. This process was repeated until a substantial amount of carbonized sample was
obtained. Carbonaceous materials produced at different temperatures and time were then characterized.
2.2 Chemical Modification of Carbonized Materials
Activation of the carbonaceous material produced using zinc chloride and hydrochloric acid was carried out in
accordance to the description reported by Yalcet al., (2000). Chemical activation using sulphuric acid was carried out
using the method adopted by Kobya, et al., 2005.
2.3 Effluent Collection
The raw effluent from an electroplating facility from a scientific development institute in Niger State, Nigeria
was collected in a sterile 4 L plastic container from the point of discharge to the environment. For preservation, 5 mL
of 2.0 M nitric acid was added perliter of the sample. The sample was refrigerated at approximately 4 C to avoid any
heavy metal precipitation and to allow the samples to be kept for further use (USEPA, 1979).
2.4 Heavy Metal Analysis
The effluent collected was analysed for presence of heavy metals (zinc, iron, copper and lead) by digesting
100ml of the effluent using 10 mL triple acid mixture (5:1:1 HNO3:HClO4:H2SO4) in a 250 mL conical flask placed in
a fume cupboard (Momodu and Anyakora, 2010). The samples were covered properly with aluminium foil to avoid
spillage and heated on a hot plate until the solution was reduced to 10 mL. The solution was then allowed to cool and it
was made up to mark with distilled water before filtering into a 50 mL standard flask, labelled and ready for further
analysis. The concentration of the heavy metals in the wastewater was determined using Atomic Absorption
Spectrometer (Perkin, 210 vgp)
IJE
RT
IJERTV3IS10190
www.ijert.org
26
k1
t
2.303
t
1
t
=
+
2
qt k 2 qe qe
Thereafter, with the data generated from the adsorption studies of the work, the parameters contained in
Langmuir, Freundlich, Termkin and Dubinin-Radushkevich adsorption isotherms were also estimated using Equations
(5), (6), (7) and (8), respectively.
qe =
q m K L Ce
1 + K L Ce
qe = k f Cen
qe =
RT
RT
lnK T +
ln Ce
b
b
lnqe = ln qD BD 2
IJE
RT
FEPA (2001)
0.30
0.01
5.0
-
FAO (1992)
0.2
2.0
-
Figure 1: Effect of agitation time (15 min - 75 min) onto 1.0 g of cassava peel (CPAC) on the removal of heavy metals
for 100 rpm agitation speed, and 298 K, pH = 2.
IJERTV3IS10190
www.ijert.org
27
The result, as presented in Figure 1, indicatedthat the rate of adsorption increased significantly for some of the
metal ions present in the electroplating wastewater between 15 60 min of the contact time. This result was found to be
important because equilibrium time was one of the important parameters required for any economical wastewater
treatment system. This trend was found to be in conformity with the observation made by Innocent et al. (2009). The
rapid initial rate increase followed by a slow rate at a later period was attributed to the availability of excess adsorption
sites on the adsorbents. The initial high adsorption rate was also discovered to be due to ion exchange followed by a
slow chemical reaction of the metal ions with active functional groups on the sample, in line with what was reported in
the work ofOkuo and Oviawe(2007). As can be seen in the figure (Figure 1), the percentage adsorption remained
constant after 60 minutes with comparatively low values (58.6%, 54.6%, 65.1%, and 80% for Cu, Zn, Fe and Pb,
respectively). This was also seen to be due to the saturation of the adsorption sites after 60 min after which little or no
increase in percentage adsorption was observed as contact time increased. CPAC was found to be efficient in the
adsorption of most of the heavy metals considered. Mostly, or at times, the observable time for maximum adsorption
was found to be between 60 - 100 min.
IJE
RT
Figure 2: Effect of CPAC adsorbent dosage (1.0 - 2.0 g) on the removal of heavy metals for agitation speed = 100 rpm,
and 298 K, pH = 2, agitation time = 60 min.
Figure 3: Effect of pH (2-7) onto 1.8 g of CPAC on the removal of heavy metals for agitation time = 60 min, 100 rpm
agitation speed, and 298 K.
IJERTV3IS10190
www.ijert.org
28
From Figure 2, it was revealed that heavy metal removal increases with increase in adsorbent. For the
adsorbents, the removal remains unchanged after 2.0 g per 20 mL of adsorbent dosage for all the metal ions. The
further increase in adsorption for Zn and Fe with adsorbent dosage was attributed to the availability of greater area and
more adsorption sites. At adsorbent dosage < 1.8 g, the adsorbent surface became saturated with the ions and the
residual ions in the electroplating water was large. With increase in the adsorption dosage, the metal ions increased due
to increased metal ion uptake by increased amount of adsorbent. At adsorbent dosage greater than 1.8 g, the increased
ion removal became very low as surface metal ion and electroplating waste water ions came in equilibrium with each
other. At about 2.0 g, the removal efficiency became almost constant. Maximum removal of the heavy metals for
CPAC was found to be 70 % for Cu, 69.5 % for Zn, 81.3 % for Fe and 100 % for Pb.
3.4 Effect of pH on Adsorption of Heavy Metals
The pH of the solution affects the surface charge of the adsorbent, as well as the degree of the ionization and
speciation of different pollutants. A change in pH affects the adsorptive process through the dissociation of functional
groups on the adsorbent surface active sites. In this work, the effect of pH was studied at room temperature by adjusting
and maintaining the pH of the wastewater to the required value (2.0, 3.0, 4.0, 5.0, 6.0 and 7.0) with a 1.0 M H2SO4
solutionand mixed with the optimum weight of the adsorbents and agitated at a preset equilibrium time. The results
obtained on the effects of pH on the quantity of heavy metal removals for CPAC are as presented in Figure 3. The
figure revealed that the maximum uptake percentage of heavy metal removal was observed at pH = 6, while lead show
no dependence on pH.
IJE
RT
Figure 4: Effect of agitation speed (100-300 rpm) onto 1.8 g CPAC on the removal of heavy metals for 60 min agitation
time, and 298 K, pH = 5.
Revealed from Figure 4was that an increase in agitation speed from 100 to 300 rpm of the wastewater did not
significantly increase the percentage removal of the metal ions, especiallyiron, copper, and zinc. Also, it was
discovered that maximum recoveries for CPAC were obtained for all the three metal ions, with 98.1% removal of
Fe(II), 99.7% of Cu(II) and 75.9% removal of Zn(II). In addition, Pb(II) was able to attain total removal of 100% even
at a lower agitation speed of 100 rpm. The increase in agitation speed resulting to the significant increase in percentage
removal of the zinc ions present in the wastewater was attributed to the fact thatthe increase in stirring rate was able to
improve the diffusion of the metal ions towards the surface of the adsorbents and also reduce the film boundary layer
surrounding the adsorbent, thereby increasing the external film mass transfer coefficient and the rate of metal
adsorption.
3.6 Adsorption Kinetics
Adsorption is a mass transfer process that involves transfer of adsorbate froma liquid phase into a solid phase.
The data obtained in this study as the dependence of adsorption capacity with time were used for kinetic analysis. The
adsorption was carried out at the optimized conditions (adsorbent dosage: 1.8 g/20 ml; agitation time: 60 min, pH: 6,
agitations speed: 250 rpm). Using the data obtained from the experiments carried out with copper, zinc and iron, noting
that lead has been eliminated from further investigations owing to its nearly constant behaviour towards most of the
IJERTV3IS10190
www.ijert.org
29
parameters investigated, the rate equations for the adsorption process were developed and shown in Figures 5 and 6
respectively are the results of the tests of pseudo-first-order rate equation (Lagergren Model) and pseudo-second-order
rate equation (Ho Model) developed based on the adsorption of the further selected heavy metals (Cu, Zn and Fe) by
the activated carbon developed from the cassava peel.
1
0.5
Cu
Log (qe-qt)
0
0
10
20
30
40
50
60
70
Zn
80
Fe
-0.5
Linear (Cu)
-1
Linear (Zn)
Linear (Fe)
-1.5
-2
Time, t (min)
IJE
RT
45
40
35
30
25
t/qt 20
15
10
5
0
Cu
Zn
Fe
Linear (Cu)
Linear (Zn)
Linear (Fe)
0
20
40
60
80
Time, t (min)
Figure 6: Pseudo-second-order reaction model for adsorption of heavy metals on CPAC
Table 2: Coefficient of Empirical Kinetic Models for CPAC
Pseudo-first-order reaction model
Adsorbent
Metal
qe,
k1 (min-1)
R12
(mg/g)
CPAC
Fe2+
-0.06448
0.964
4.965
CPAC
Cu2+
0.039151
0.988
1.972
CPAC
Zn2+
0.057575
0.999
3.199
It was discovered from the results of the fittings, carried out using Equations (3) and (4) for the pseudo-firstorder and the pseudo-second-order reaction models, shown in Figures 5 and 6, respectively, that the pseudo-first-order
reaction model (Lagergren Model)used yielded good straight lines for the copper, zinc and iron investigated compared
to the pseudo-second-order reaction model, which was significantly scattered except for copper. Also, as given in Table
IJERTV3IS10190
www.ijert.org
30
2, the squares of the regression correlation coefficients of the developed pseudo-first-order reaction models for the three
metals were found to be very close to unity while for those (squares of the regression correlation coefficients) of the
pseudo-second-order rate equation, it was only that of copper that was very close unity.
Thus, the valid applicability of the developed pseudo-first-order reaction model for the adsorption of heavy
metals by the produced activated carbon from cassava peel has been well confirmed. Karthika, et al.(2010) reported
similar results of kinetic studies when sago waste (prepared from cassava roots) was utilized as an adsorbent for the
removal of heavy metals from aqueous solutions.
3.7 Adsorption Isotherms
Equilibrium analysis has been carried out on the data dependence of adsorption capacity to initial copper, zinc
and iron concentration. The data were obtained from the adsorption of copper, zinc and iron from 20 mL of
electroplating water using 1.8 g activated cassava char, CPAC at 60 min agitation time and pH = 5.
16.000
y = 0.976x + 5.311
R = 0.834
14.000
12.000
Ce/Qe
10.000
y = 2.189x + 3.781
R = 0.912
Cu
Fe
8.000
Zn
6.000
Linear (Cu)
4.000
Linear (Fe)
Linear (Zn)
IJE
RT
2.000
y = 0.117x - 0.015
0.000
R = 0.685
2.000
-2.0000.000
4.000
6.000
8.000
10.000
Ce
-1.500
-1.000
-0.500-0.2000.000
0.500
1.000
1.500
Log qe
-0.400
-0.600
Cu
-0.800
Fe
-1.000
Zn
-1.200
Linear (Cu)
-1.400
Linear (Fe)
-1.600
Linear (Zn)
-1.800
-2.000
Log Ce
IJERTV3IS10190
www.ijert.org
31
3.000
R = 0.862
2.000
1.000
Cu
R
R == 0.930
0.458
Ln Ce
Fe
Zn
0.000
0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800
-1.000
Linear (Cu)
Linear (Fe)
Linear (Zn)
-2.000
-3.000
qe
2000.0
4000.0
6000.0
8000.0
-1.000
Cu
-2.000
-2.500
-3.000
-3.500
-4.000
Fe
IJE
RT
Lnqe
-1.500
Zn
Linear (Cu)
y = -5.99E-04x - 5.81E-01
R = 9.37E-01
Linear (Fe)
Linear (Zn)
y = -4.56E-04x - 9.80E-01
R = 9.66E-01
-4.500
RTln(1+(1/Ce)
Freundlich
Termkin
IJERTV3IS10190
Constants
qm
KL
R2
kf
n
R2
KT
B
R2
Value
Unit
mgg-1
Lmg-1
mgg-1
Lmg-1
-
www.ijert.org
Cu2+
1.0245
0.1838
0.834
0.1483
1.471
0.994
1.3962
15582.214
0.862
Fe2+
8.5470
-7.8000
0.685
0.0925
1.488
0.735
11.3127
45880.963
0.458
Zn2+
0.4568
0.5789
0.912
0.1507
1.355
0.958
11.4730
33034.293
0.930
32
Dubinin-Radushkevich
E
qD
B
R2
KJmol-1
mgg-1
mol2KJ-2
-
28.8916
0.5593
0.000599
0.937
56.0772
0.4804
0.000159
0.667
33.1133
0.3753
0.000456
0.966
Adsorption isotherm model parameters estimated using the expressions given in Equations (5), (6), (7) and (8)
for Langmuir, Freundlich, Termkin and Dubinin-Radushkevich adsorption models respectively were reported in Table
3.It was discovered that the values of the Langmuir constant, qm, computed which were obtained to be 1.0245, 8.5470
and 0.4568 mgg-1 indicated thatits adsorption was the best at low concentration of Cu2+, Fe2+, and Zn2+ compared to
those obtained from Freundlich constant,Kf,which were 0.1483, 0.0925 and 0.1507 mgg-1, and Dubinin-Radushkevich
constant, qD, which were0.5593, 0.4804 and 0.3753 mgg-1, respectively for Cu2+, Fe2+, and Zn2+.However, considering
the square of the correlation coefficients (R2), it was observed that the results fitted best with Freundlich model among
all the models considered. In addition, the Freundlich constant, n, which was estimated to be greater than 1 also
confirmed its adequacy for describing the adsorption of heavy metals from the electroplating wastewater usingcassava
peel activated carbon.
4.0 CONCLUSIONS
The results obtained from this work have revealed that between the two kinetic (pseudo-first-order and
pseudo-second-order) models analysed for the adsorption of copper, zinc, lead and iron ion from electroplating
wastewater onto the surface of the developed cassava peel activated carbon, pseudo-first-order model was found to
represent the process better. Furthermore, considering the four isotherm models that were used to fit theequilibrium
data generated from the process, Freundlich isotherm model was discovered to best because of its very high square of
correlation coefficients for the three heavy metals considered.
IJE
RT
NOMENCLATURES
b
Langmuir constant (energy of adsorption) (L/mg)
Ce
Concentration of metal ions in solution (mol/L) at equilibrium,
Co
Initial metal ion concentration (mol/L)
CPAC Cassava peel activated carbon
Ct
Concentration of metal ions in solution at time t (mol/L)
FAO
Food and Agriculture Organization
FEPA Federal Environmental Protection Agency
k1
Adsorption rate constant of pseudo-first-order kinetic model (min-1)
k2
Adsorption rate constant of pseudo-second-order kinetic model (g mg-1 min-1)
Kf
Freundlich constant related to adsorption capacity
KL
Constant related to the affinity of the binding sites and energy of adsorption (L/mg)
KT
Temkin equilibrium binding constants corresponding to the maximum binding energy (L/mg)
M
Mass of adsorbent used (g)
n
Freundlich constant related to adsorption intensity
q
Amount of heavy metal ions adsorbed at time t, mgg-1
qD
Adsorption capacity (mg/g)
qe
Amount of heavy metals adsorbed at equilibrium time mgg-1
qm
Langmuir constant (adsorption capacity) (mg/g)
R
Universal gas constant (Jmol-1K)
T
Absolute temperature (K)
t
Time, min
USEPA United States Environmental Protection Agency
V
Volume of initial metal ions solution used (L)
Polanyi potential
REFERENCES
(1) Demirbas, A. (2004). Adsorption of lead and cadmium ions in aqueous solutions onto modified lignin from
alkali glycerol delignication. Journal of Hazardous Materials, 109, 221-226.
(2) FAO (Food and Agriculture Organization). 2006. Statistical database of food and Agricultural Organization of
the United Nations. Available at http://faostat.fao.org/ (accessed august 2007; verified 2 August2008). FAO,
Rome.
(3) FEPA (Federal Environmental Protection Agency). (2001). Federal Ministry of Environment. National
Guidelines and standards for water in Nigeria, Lagos, Nigeria; Federal environmental protection Agency.
(4) Gupta, V.K., Gupta, M. and Sharma, S. (2001). Process development for the removal of lead and chromium
from aqueous solution using red mud an aluminum industry waste. Water Resource, 35(5), 1125 1134.
IJERTV3IS10190
www.ijert.org
33
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
IJERTV3IS10190
Horsfall Jr., M., Ayebaemi, I. and Abi, A.A. (2004). Studies on the influence of mercaptoacetic acid (MAA)
modification of cassava (ManihotSculentaCranz) waste biomass on the adsorption of Cu2+ and Cd2+ from
aqueous solution. Bulletin of the Korean Chemical Society, 25(7), 969-976.
Innocent, O., Emmanuel, A. and Thomas, A. (2009). Biosorption of heavy metal ions from aqueous solutions
using a biomaterial. Leonardo Journal of Sciences, 58-65
Jang, Y.S. and Park S.J. (2001). Pore structure and surface properties of chemically modified activated carbon
for adsorption mechanism and rate of Cr(VI). Online. Http: // www.idealibrary.com.
Karthika, C., Vennilamani, N., Pattabhi, S. and Sekar, M. (2010). Utilization of sago waste as an adsorbent for
the removal of Pb (II) from aqueous solution: kinetic and isotherm studies. International Journal of Engineering
Science and Technology, 2(6), 1867-1879
Klaassen, C.D., Hardmen, J.G., Limbird, L.E., Gilman, A.G. (2001). The Pharmacological Basis of
Therapeutics. McGraw Hill, New York, pp. 1851-1875.
Kobya, M., Demirbas, E., Senturk, E. andInce, M. (2005). Adsorption of heavy metal ions from aqueous
solutions by activated carbon prepared from apricot stone. Bioresource Technology, 96, 1518-1521.
Abdullah, L.C., Mohammed, Saidatal, S.J and Choong,T.S.Y. (2010). Modelling of single and binary solutions
of heavy metals unto activated carbon- equilibrium studies. Pertanika J. Sci and Technology, 18, 83-93.
Mohanty, K., Jha, M., Meikap, B. C. and Biswas, M.N. (2005). Removal of Cr (VI) from dilute aqueous solution
by activated carbon from Terminaliaarjuna nuts activated zinc chloride. Chemical Engineering Science, 60,
3049-3059.
Momodu, M.A. and Anyakora, C.A. (2010). Heavy metal contamination of ground water: Surulere case study.
Research Journal Environmental and Earth Sciences, 2(1), 39-43.
Nourouzi, M., Chuah, T. and Choong, T. (2009). Equilibrium and kinetic study on reactive dyes adsorption by
palm kernel-shell based activated carbon in single and binary system. Journal of Environmental Engineering,
135, 1393-1398.
Okuo, J. and Oviawe, A.P. (2007). Selection sorption of mixed heavy metal ions using fibre modified with citric
acid. Journal of Chemistry Society of Nigeria, 32(2), 247-253.
USEPA (United States Environmental Protection Agency). (1979). Human Health Effects of Molybdenum in
Drinking Water. EPA, 65-77.
Yalc, N.andSevinc, V. (2000). Studies of the surface area and porosity of activated carbons prepared from rice
husks, Carbon 38, 1943-1945.
IJE
RT
(5)
www.ijert.org
34